Reaction product of aldehydes and triazine derivatives



Patented my 13, 1943 UNITED STATES PATENT OFFICE--- 'REACTION PRODUCT OF ALDEHYDES AND TRIAZINE DERIVATIVES Gaetano F. DAlelio, Pittsfleld, Mass, assignor to General Electric Comp New York any, a corporation of No Drawing. Application April 17, 1942,

Serial No. 439,390

20 Claims.

, This invenidon relates to the production or new- 7 synthetic materials and more particularly to new reaction products of particular utility in the plastics and coating arts. Specifically the invention is concerned with emnpositions of matter comprising a condensafion product of ingredients comprising an aldehyde, including po1ymeric= aldehydes and aldehyde-addition products, e. g., formaldehyde, urea, trimemylol melamine, etc, and a, triazine derivative col-smiling to the following general iormuL:

This application is a continuation-in-part oi my g application Serial No. 436,955, filed March 31, 1942, and assigned to the same assignee as the t invention.

halogenosubstituted hydrocarbon radicals are chloromethyl, chloroethyl, chlorophenyl, di chlorophenyl, chlorocyclohexyl, ethyl chloroparaformaldehyde, dimetliyiol In the above formula 11 represents an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, Z Iepresenin a member of the class consisting of oxygen and sulfur, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and substituted hydrocarbon radicals, more particularly halo-hydrocarbon radicals.

Illustrative examples of monovalent radicals.

that B in Formula I may represent are aliphatic (e. g., methyl, ethyl, propyl, isopropyl, butyl, secfluorim or iodine atom. Specificexamples of phenyl, phenyl chloroethyl, bromoethyl, bromopropyl, fiuorophenyl, iodophenyl, bromotolyl, etc.

Preferably R in Formula I is hydrogen. 7 Also especially suitable for use in carrying the present invention into efiect are 'triazine derivatives corresponding to the general formulas:

and, more particularly,

in NHR 2 s u i u RHNC c-s cH=cNH-c-NHR where x, Z and R-have the same meanings as given above with reference to Formula I.

Instead of the symmetrical triazines (s-triazines) represented by the above formulas, corresponding derivatives of the asymmetrical and vicinal triazines may be used.

The triazine derivatives that are used in carrying the present invention into effect are more fully described and are specifically claimed in my above-mentioned; copending application Serial No. 436,955. As pointed out in this copending application, a suitable method of preparing the triazine derivatives employed in practicing the present invention comprises effecting reaction between a mercapto triazine and a mon0-halogenated acylated orthionoacylated urea or thiourea. in the presence of a hydrohalide acceptor, e. g., an alkali-metal hydroxide.

Specific examples of compounds embraced by Formula I (these compounds are s-triazinyl thio acyl or thionoacyl ureas or thioureas) that may be used in producing my new condensation products are listed below: v

Monoamino s-triazinyl di-(thio acetyl thiourea) Monoamino s-triazinyl di-(thio thionoacetyi urea) Diamino s-triazinyl Mdnoamino thiourea) 1 Monoamino s triazinyl di-(alpha-thio propionyl urea) Monoamino s-triazinyl di-(beta-thio propionyl ureal Monoamino s-triazinyl dl- (alpha-thio propionyl thiourea) Monoamino s triazinyl di-(beta-thio propionyl thiourea) v Monoamino s-triazinyl di-(alpha-thio thionopropionyl urea) Monoamino s-triazinyl di-(beta-thio thionopropionyl urea) Y Monoamino s-triazinyl di-(alpha-thio thionopropionyl thiourea) Monoamino s-triazinyl di-(beta-thio thionopropionyl thiourea) 's-Triazinyl-2,4,6 .tri-(beta-thio propionyl' thiourea) s-'Iriazinyl-2,4,6 tri-(alpha thio thionopropionyl urea) s-Triazinyl-2,4,6 tri-(beta thio thionopropionyl urea) 's triazinyl di-(thio thionoacetyl V "4,6-dianilino s-triazinyl-Z N-(beta-thlo gammas-Triazinyl-2 ,4,6 tri-(alpha-thio thionopropionyl thiourea) s-'Ifriazinyl- 2,4,6 tri-(beta-thio thionopropionyl thiourea) Diamino s-triaz inylgimono-(alpha-thin propionyl urea) a Diamino s-trlazinyl mono-(beta-thio propionyl urea) Diamino s-triazinyl mono- (alpha-thio propionyl thiourea) v mono-(beta-thio propion'yl thiourea) Diamino s-triazinyl mono-(alpha-thio thionopropionyl urea) Diamino s-triazinyl mono-(beta-thio thionopropionyl urea) Diamino s-trlazinyl mono-(alpha-thio thinnepropionyl thiourea) Diamino s-triazinyl mono-(beta-thio thionopropionylthiourea) Diamino s-triazinyl mono-(alpha-thio valeryl urea) Diamino s-triazinyl mono-(beta-thi valeryl urea) Diamino s-triazinyl mono-(alpha-thio valeryl thiourea) Diamino s-triazinyl mono-(beta-thio valeryl thiourea) 6-amino s-triazinyl 2-(thio acetyl urea) 4-. (betas triazinyl 2 thin s-triazinyl-2 alpha-thio s triazinyl 2 -4,6-dl- (methylamino) s-triazinyl-2 beta-thio alpha-phenyl butyryl urea cyclohexyl butyryl) N '-methyl thiourea 4,6-diamino s-triazinyl-Z N-(alpha-thio pro- 's-Triazinyl-2,4,6 tri-(beta-thio alpha-phenyl butyryl thiourea) 6-amino s-triazinyl 2-(thio thionoacetyl urea) Diamino s-triazinyl alpha-thio beta-fluorophenyl propionyl urea Diamino s-triazinyl beta-thio alpha-bromopropyl propionyl thiourea The present invention is based on my discovery that new and valuable materials of particular utility in the plastics and coating arts can be produced by eflecting reaction between ingredients comprising essentially an aldehyde, in-

acetyl urea) 4-(thio eluding polymeric aldehydes, hydroxyaldehydes' and aldehyde-addition produ'cts, and triazine. derivatives of the kind embraced by Formula I, numerous examples of which have been given above and in my above-identified copending application.

Resins heretofore have been made by condensing an aldehyde with a thioammeline ether such. for example, as a bisthioammeline polyalkylene ether, but such resins are not entirely satisfactory for use in many applications, for instance in the production of molding compounds having a high plastic flow during -molding combined .with a rapid cure to an insoluble, infusible state. Surprisingly it was found that the heat-curable resinous condensation products or thi invention to heat and abrasion, and therefore are especially suitable for use where optimum heatand abrasion-resistance are of primary importance.

In practicing my invention the initial condensation reaction may be carried out at normal or at elevated temperatures, at atmospheric, subatmospheric or super-atmospheric pressures, and

1 under neutral, alkaline or acid conditions. Preterably the reaction betweenthe components is initiated under alkaline conditions.

Any substance yielding an alkaline Or an acid aqueous solution may be used in obtaining alkaline or acid conditions 'for the initial condensation reaction. For example, I may use an alkaline substance such as sodium, potassium or calcium hydroxides, sodium or potassium carbonates, mono-, dior trl-amines, etc. In some cases it is desirable to cause the initial condensation reaction between the components to take place in the presence of a primary condensation catalyst and a secondary condensation catalyst. The primary catalyst advantageously is either an aldehyde non reactable nitrogen containing.

basic tertiary compound, e. 3., tertiary amines such as trialk'ylfe. g., trimethyl, triethyl, etc.) amines, triaryl (e. g., triphenyl, tritolyl, etc.) amines, etc., or an aldehyde-reactable nitrogencontaining basic compound, for instance ammonia, primary amines (e. g., ethyl amine, propyl amine, etc.) and secondary amines (e. g., dipropyl amine, dibutyl amine, etc.). The secondary condensation catalyst, which ordinarily is used in an amount less than the amount of the primary catalyst, advantageously is a fixed alkali, forinstance a carbonate, cyanide or hydroxide of an alkali metalie. g sodium, potassium, lithium,

etc). Y

Illustrative examples of acid condensation catalysts that may be employed are inorganic or organic acids such as hydrochloric, sulfuric,

phosphoric, acetic, lactic, acrylic,'malonic, etc.,.

or acid salts such as sodium acid sulfate, monoamino s-triazinyl thio thiono'acetyl thioura,

13 amino s-triaziny1, thiothionacetyl urea, di=- thermosetting or potentially thermosetting bodsodium phosphate, monosodium phthalate, etc.

Mixtures of acids, of acid salt or of acids and" of acid salts may be employed if desired.

The reaction between the aldehyde, e. g., formaldehyde, and the triazine derivative may be carried out in the presenceof solvents or diluents, fillers, other natural or synthetic resinous bodies, or while admixed with other materials that also can react with the aldehydic reactant or with the triazine derivative, e. g., ke-

tones, urea (NI-IzCONI-Iz), thiourea, selenourea,

iminourea (guanidine), substituted ureas, thioureas, selenoureas and iminoureas, numerous examples of which are given in various copending applications of mine, for instance in my copending application Serial No. 363,037, filed October 26, 1940; monoamides of monocarboxylic and polycarboxylic, acids and polyamides of polycarboxylic acids; e. 'g., acetamide, halogenated acetamides (e. g., a chlorinated acetamide) mal'eic monoamide, malonlc monoamide, phthalic monoamide, maleic diamide, fumaric diamide, malonic diamide, itaconic diamide, succinic diamide, phthalic diamide, the monoamide, diamide and triamide of tricarballylicacid, etc.; aldehyde-reactable triazines other than the triazine derivatives constituting the primary components of the resins of the present invention, e. g., melamine, ammeline, ammelide, melem, melam, melon, numerous other examples being given in various copending applications of mine, for instance in application Serial No. 377,524, filed February 5, 1941, and in applications referred to in said copending application; phenol and substituted phenols, e. g., the cresols, the xylenols, the tertiary alkyl phenols and numerous other phenols such as mentioned in my Patent No. 2,239,441; monohydric and -polyhydric alcohols, e. g., butyl alcohol, amyl alcohol, isoamyl alcohol, ethylene glycol, glycerine, polyvinyl alcohol, etc.; amines, including aromatic amines, e. g., aniline, etc.; and the like.

The modifying reactants may be incorporated with the triazine derivative and the aldehyde by mixing all the reactants and effecting condensation therebetwee'n or by various permutations of reactants as described, for example, in my copending application Serial No. 363,037 with particular reference to reactions involving a urea, an aldehyde and a semi-amide of oxalic acid. For instance, I may form a partial condensation product of ingredients comprising (1) urea or melamine or urea and melamine, (2) a triazine derivative of the kind described'herein and in my copending application Serial No. 436,955, for example diamino s-triazinyl thio acetyl urea, diamino s-triazinyl thio acetyl thiourea, di-

ies that convert under heat or under heat and pressure to an insoluble, infusible state. The thermoplastic condensation products are of particular value as plasticizers for other synthetic resins. The thermpsetting or potentially thermosetting resinous condensation products, alone or mixed with fillers, pigments, dyes, lu-

bricants, plasticizers, curing agents, etc., may be used, for example, in the production of molding c0mpositl0ns w Depending upon the particular conditions of reaction and the particular reactants employed, the intermediate or partial condensation products vary from clear, colorless or colored, syrupy, water-soluble liquids to viscous, milky dispersions and gel-like masses of decreased solubility in ordinary solvents, e. g., ethyl alcohol, butyl alcohol, ethylene glycol monoethyl ether, ethylene glycol, glycerine, etc. These liq'uid intermediate condensation products may be concentrated or diluted further by the removal or addition of volatile solvents to form liquid coating compositions of adjusted viscosity and concentra tions. The heat-convertible or potentially heatconvertible resinous condensation products may be used in liquid state, for instance as surfacecoating materials, in the production of paints, varnishes, lacquers, enamels, etc., for general adhesive applications, in producing laminated articles and for numerous other purposes, The liquid heat-hardenable or potentially heat-hardenable condensation products also. may be used directly as casting resins, while those which are of a gel-like nature in partially condensed state may be dried and granulated to form clear, unfilled heat-convertible resins.

In order that those skilled in the art better may understand how this invention may be car ried into efiect the following examples are given by way of illustration. All parts are by weight.

Example 1 Parts Diammo s-triazlnyl thio acetyl urea 6.1 Aqueous formaldehyde (approx. 37.1

HCHO) 20.3

Aqueous ammonia (approx. 28% NH3) 0.5 Aqueous solution of sodium hydroxide Example 2 Parts Diamino s-triazinyl thio acetyl urea 6.1 Urea 15.0 Aqueous formaldehyde (approx. 37.1%

HCHO) 48.6 Aqueous ammonia (approx. 28% NHJ) 3.0 Aqueous solution of sodium hydroxide (0.5 N) 1.6 chloroacetamide (monochloroacetamide) 0.4

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 13 minutes. now added and refluxing was continued for an additional 2 minutes to cause it to intercondense with the partial condensation product of urea, diamino s-triazinyl thio acetyl urea and formaldehyde. A' molding (moldable) composition was made from the resulting resinous syrup by mixing therewith 24.8 parts alpha cellulose in flock form and 0.1 part of a mold lubricant, specifically zinc stearate. The wet molding compound was dried at room temperature until suflicient moisture had been removed to provide a material that could be molded satisfactorily. A, sample of the dried and ground molding compound was molded for 5 minutes "at 140 C. under a pressure of 11,250

pounds per square inch. The molded piece was well cured throughout and had a well-knit and homogeneous structure. to water as shown by the fact that it absorbed only 3.5% by weight of water when immersed in boiling water for minutes, followed by immersion in cold water for 5 minutes. (When similarly tested for water resistance, molded articles made from the ordinary urea-formaldehyde molding compositions absorb about 5 to 7% by weight of water.) The molding compound had very good flow characteristics during molding as indicated by the 'amount'of flash on the molded piece and the evenness or homogeneity of structure of the molded article.

Instead of using chloroacetamide in accelerating the curing of the potentially reactive resinous material, heat-convertible compositions may be produced by adding to the partial condensation, product (in syrupy or other form) direct or active curing catalystsle. g., citric acid, phthalic anhydride, malonic acid, oxalic acid, etc.), or latent curing catalysts (e. g., sodium chloroacetate, N-diethyl chloroacetamide, glycine ethyl ester hydrochloride, etc.) or by intercondensation with curing reactants other than monochloroacet'amide (e. g., diand tri-chloroacetamides, chloroacetanitriles, alpha, beta-dibromopropionitrile, aminoacetamide hydrochloride, ethylene diamine mono hydrochloride, the ethanolamine hydrochlorides, nitrourea, chloroacetyl urea, chloroacetcne, glycine, sulfamic acid, citric diamide, phenacyl chloride, etc.). Other examples of active and latent curing catalysts and of curing reactants that may be employed to accelerate or to effect the curing of the thermosetting or potentially t-hermosetting The chloroacetamide was It had good resistance resins of this example, as well as examples that follow, are given in various copendlng applications of mine, for instance in copending applications Serial No. 346,962, filed July 23, 1940, and Serial No. 354,395, filed August 27, 1940, both of which applications are assigned to the same assignee as the present invention. I

Aqueous formaldehyde (approx, 37.1%

HCHO) 40.5

Aqueous ammonia (approx. 28% NHJ) 1.7 Aqueous solution of sodium hydroxide (0.5 N) 1.3 Chloroacetamide 0.2

I All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 5 minutes. The chloroacetamide, was now added and the resulting resinous syrup immediately was mixed with 20.4 parts alpha cellulose and 0.1 part zinc stearate to form a molding compound. The wet molding composition was dried at room temperature as described under Example 2. A sample of the dried and ground molding compound was molded into the form of a disk, using a molding time of 5 minutes, a molding temperature of C. and a molding pressure of 5,600 pounds per square'inch. The molded disk was extracted hot from the mold and did not warp or become distorted upon cooling to room temperature. The molded piece was well cured and had a well-knit and homogeneous structure. It had excellent resistance to water, absorbing only 0.52% by weight of water when tested for its water-resistance characteristics as described under Example 2. The molding compound flowed satisfactorily during molding.

Example 4 i 7 Parts Diamino s-triazinyl thio acetyl urea 6.1 Dimethylol urea (commercial grade contain-' ing approx. 11% by weight of water) 27.0

Aqueous ammonia (approx. 28% NHa) 1.7

Aqueous solution of sodium hydroxide (0.5 N) 1.3 Water--- 36.3 02

Chloroacetamide were heated together under reflux for 7 minutes at the boiling temperature of.the mass, yielding a resinous syrup that was mixed with 24.2 parts alpha cellulose and 0.1 part zinc stearate to form a molding compound. The wet molding composition was dried at room temperature as described under Example 2. A sample of the dried and ground molding compound was molded for formula, an equivalent amount of a methylol melamine, preferably a polymethylol melamine such as trimethylol melamine, melamine, etc., may be employed.

hexamethylol Example 5 Q E:mmple 7 I Parts p t Diamino s-triazinyl thio acetyl urea 6.1 Diamino s-triazinyl thio acetyl urea 4.84 Aminotriazole, specifically l-phenyl guana- Furfura v 19.6

zol 17.5 5 Aqueous ammonia (approx. 28% NR3) 0.22 Aqueous formaldehyde (approx. 37.1% Aqueous solution of sodium hydroxide HCHO) 48.6 0.5 N) 0.8 Aqueous ammopla' (approx NH3) "7" were heated together under reflux at the boiling Aqueous solution .of sodium hydroxide 10 temperature or the massyielding a resinous N) syrup that hardened toan infusible mass when a Chloroacetamide 0.2

minutes at 140 C. under 'a pressure of. 4,500.

pounds per square inch. A well-cured molded piece having a well-knit and homogeneous structure was obtained. When tested for its waterresistance characteristics as described under Example 2, the molded article absorbed only 3.95% by weight of water. The molding compound showed satisfactory plastic flow during molding.

' Example 6 a Parts Diamino s,-triazinyl thio acetyl urea 12.1 Aqueous formaldehyde (approx; 37.1%

HCHO) 40.5 Aqueous ammonia (approx. 28% NH3) 1.0

Aqueous solution of sodium hydroxide I Chloroacetamide 0.2

All of the above ingredients with the exception of the chloroacetamide were heated together under reflux at the boiling temperature of the mass for 10 minutes. The chloroacetamide was now added and refluxing was continued for an additional 4 minutes to cause the chloroacetamide to intercondense with the partial condensation product of the formaldehyde and diamino s-triazinyl thio acetyl urea. The resulting resinous syrup was mixed with 18.3 parts alpha cellulose and 0.1 part zinc stearate to form a molding compound. The wet molding composition was dried at room temperature as described under Example 2. A sample of the dried and ground molding compound was molded for 5 minutes at 140 C. under a pressure of 4,500 pounds per square inch. The molded piece was removed hot from the mold and didnot warp or become distorted upon cooling to room temperature. 'It was well cured throughout, had a heating on a 140 C. hot plate.

homogeneous'and well-knit structure and good resistance to water as shown by the fact that it absorbed only 2.4% by weight of water when tested for its water-resistance characteristics as described under Example 2. The plastic flow of the molding compound during molding was very good, being better in this respect than the mold-.- ing compounds of Example 2, 3, 4 and 5. Instead of using chloroacetamide as a curing reactant to accelerate the curing of the potentially heat-curable resin, other curing agents such as mentioned under Example 2 may be employed.

sample of it was heated on a C. hot plate. The cure of the resin to the infus'ible state was accelerated by adding glycine, chloroacetamide, aminoacetamide hydrochloride and other curing agents such as mentioned under Example 2 to the syrupy condensation product, followed by The resinous composition of this example is suitable for use in the preparation of molding compounds and molded articles.

Aqueous solution of sodium hydroxide (0.5 N)- 0.8 Water 17.2

were heated together under reflux at theboiling temperature of the mass for 10 minutes. When a sample of the resinous material produced in this manner was heated on a 140 C. hot plate, it formed a pliable but infusible film. The cure of the resin to the infusible state was accelerated by adding phthalic monoamide, chloroacetamide, phenacyl chloride and other curing agents such as mentioned under Example 2 to the syrupy condensation product, followed by heating on a 140 C. hot plate. The resinous product of this example may be used in the preparation of liquid coating materials or in the manufacture of molding compounds.

Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature of the mass for 10 minutes. The resulting resinous syrup was dehydrated by heating it on a steam plate. The dehydrated syrup was found to be soluble in ethylene-glycol monoethyl ether and benzyl alcohol. The solubility and film-forming characteristics of the resinous composition of this example make it especially suitable for use in the preparation of coating and impregnating compositions. For example, it may be used in the production of spirit and baking varnishes. It may be used as a modifier of varnishes of the aminoplast and alkyd-resin types.

Example 10 Parts Diamino s-triazinyl thio acetyl urea 4.84 Acct- 2.36 Aqueous formaldehyde (approx. 37.1%

' HCHO) 16.2 Aqueous solution of sodium hydroxide (0.5 N) 0.8 Aqueous'ammom'a (approx. 28% N113)..-" 0.25

were heated together under reflux at the boiling temperature of the mass for 7 minutes, yielding a resinous syrup that formed a pliable resin film when a sample of the syrup was heated on a 140 C. hot plate. The resinous composition of this example is suitable for use as a modifier ofless plastic resins to improve their flow or, plasticity characteristics. It also may be employed in the preparation of thin, molded plastic materials, for example flexible covers and novelty articles that are made in thin cross-sections.

Emmpl 11 Parts Diamino s-triazinyl thio acetyl urea 4.84 Diethyl malonate 2.40 Aqueous formaldehyde (approx. 37.1%

ECHO) -16.2 Aqueous ammonia (approx, 28% NI-Ia) 0.25

Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature of the mass for minutes. Upon heating a sample of the resulting resinous syrup on a 140 C, hot plate, it bodied to a thermoplastic resin that is suitable for use as a flow extender of less plastic resins as described above with reference to the product of Example 10.

Aqueous solution of sodium hydroxide were heated together under reflux at the boiling temperature of the mass for 7 minutes. The resulting resinous syrup was dehydrated on a steam plate. The dehydrated syrup was soluble in ethylene glycol, ethylene glycol monoethyl ether and benzyl alcohol. When the dehydrated syrup was treated with a curing agent, specifical- 17 a small amount of hydrochloric acid, and the resultingproduct baked in film form on a glass surface for several hours at 70 C., a baked film that was hard, transparent, smooth and waterresistant was obtained. The resinous composition of this example is especially suitable for use in the manufacture of coating and impregnating compositions.

were heated together under reflux at the boiling temperature of the mass for 6 minutes. When a sample of the resulting resinous syrup was heated on a 140 C. hot plate, it formed an infusible sheet that did not adhere to the hot plate. less flexible films, more advanced in cure, are produced by similarly heating samples of the syrup in which has been incorporated chloroaeetamide, glycine or other curing agent such as mentioned under Example 2'. When a sample of the syrupy resin was applied to a glass plate, which then was baked for several hours at 70 C.,

resistant film was formed on the plate. The resinous composition of this example may be used in the production of molding compositions and molded articles. It also may" be employed" in the manufacture of various liquid coating and impregnating compositions.

It will be understood, of course, by those skilled in the art that my invention is not limited to condensation products-obtained by reaction of ingredients comprising an aldehyde and the specific triazinyl compound named in the aboveillustrative examples. Thus,- instead of diamino s-triazinyl thio acetyl urea Imay use, for example, di-

amino s-triazinyl thio acetyl thiourea, diamino striazinvl, thio thionoacetyl urea, diamino s-triazinyl thio thionoacetyl thiourea,.monoamino striazinyl di-(thio acetyl urea), s-triazinyl-2,4,6

'tri-(thio acetyl urea) or any other triazine deriv- I prefer to use as the aldehydic reactant formaldehyde or compounds engendering formaldehyde,

e. g., paraformaldehyde, hexamethylene tetramine, etc. Illustrative examples of other aldehydes that may be used are acetaldehyde, propionaldehyde, butyraldehyde, methacrolein, crotonaldehyde, octaldehyde, benzaldehyde, furfural, etc., mixtures thereof, or mixtures of formaldehyde (or compounds engendering formaldehyde) with such aldehydu. Illustrative examples of aldehyde-addition products that may be employed instead of the aldehydes themselves are the monoand poly-(N-carbinol) derivatives, more particularly the monoand poly-methylol derivatives, of urea, thiourea, selenourea and iminour'ea, substituted ureas, selenoureas, thioureas and iminoureas (numerous examples of which are given in my copending application Serial No. 377,524), monoand p0lv-(Ncarblnol) derivativesof amides of polycarboxylic acids, e. g., maleic, itaconic, fumaric, adipic, malonic, succinic, citric, phthalic, etc., monoand poly-(N-carbinol) derivatives of the aminotriazoles, monoand poly-(N-carbinol) derivatives of the aminodiazines, etc. Particularly good results are obtained with active methylene-containing bodies such as a methylol urea, more particularly monoand dimethylol ureas, and a methylol melamine, e. g., monomethylol melamine and polymethylol melamines (di-, tri-, tetra-, pentaand hexa-methylol melamines) Mixtures of aldehydes and aldehyde-addition products may be employed, e. g., mixtures of formaldehyde and methylol compounds such, for instance, as dimethylol urea, trimethylol melamine, hexamethylol melamine, etc.

The ratio of the aldehydic reactant to the triazine derivative may be varied over a wide range, but ordinarily the reactants are employedin an amount corresponding to at least one mol of the aldehyde, specifically formaldehyde, for each mo] a hard, adhering, opaque, smooth, white, water- 16 of the triazine derivative. Thus, I may use, for example, from one to eight or nine or more mols of an aldehyde for each mol of triazine derivative. Good results are obtained in manufacturing thermosetting. resinous compositions using from about 2% to 4% mols aldehyde, specifically formaldehyde, for each mol of triazine derivative. When he aldehyde is available for reaction in the etc.

ylol urea, trimethylol melamine, etc., then higher.

amounts of such aldehyde-addition products are used, for instance from 3 or 4 up to or or condensation between the primary components. Thus, as modifying agents I may use, for instance,

'monohydric alcohols such as ethyl, propyl, isopropyl, isobutyl, hexyl, etc., alcohols; polyhydric alcohols such as diethylene glycol, triethylene glycol, pentaerythritol, etc.; amides such as formamide, stearamide, acrylamide, benzamide, toluene sulfonamides, benzene sulfonamides, adipic diamide, phthalamide, etc.; amines such as ethylene diamine, phenylene diamine, etc.; phenol and substituted phenols, including aminophenols, etc.; ketones, including halogenated ketones; nitriles, including halogenated nitriles, e. g., acrylomtrile, methacrylonitrile, succinonitrile, chloroacetonitriles, etc.; aoylated ureas, more particularly halogenated acylated ureas of the kind described, for example, in my copending applications Serial No. 289,273, filed August 9, 1939, now Patent No. 2,281,559, issued May 5, 1942, and Serial No. 400,649, filed July 1, 1941 now Patent No. 2,294,873, issued September 1, 1942; and others.

The modifying bodies also may take the form of high molecular weight bodies with or without resinous characteristics, for example, hydrolyzed wood products, formalized cellulose derivatives, lignin, protein-aldehyde condensation products, aminodiazine-aldehyde condensation products, aminotriazole-aldehyde condensation products, Other examples of modifying bodies are the urea-aldehyde condensation products, the aniline-aldehyde condensation products, furfural condensation products, phenol-aldehyde condensation products, modified or unmodified, saturated or unsaturated polyhydric alcohol-poly-car-.

boxylic acid condensation products, water-soluble cellulose derivatives, natural gums and resins such as shellac, rosin, etc. polyvinyl compounds such as polyvinyl esters, e. g., polvinyl acetate, polyvinyl butyrate, etc., polyvinyl ethers, including polyvinyl acetals, specifically polyvinyl formal, etc.

Instead of effecting reaction between a triazine derivative of the kind herein described and an aldehyde, specifically formaldehyde, I may cause andunmodifled resinous compositions of this invention have a wide variety of uses. For example, in addition to their use in flying bodies before, during or after eifecting.

the production of molding compositions, they may be used as modifiers of other natural and synthetic resins, as laminating varnishes in the production of laminated articles wherein sheet materials, e. g., paper, cloth, sheet asbestos, etc., are coated and impregnated with the resin, superimposed and thereafter united under heat and pressure. They may be used in the production of wire and bakingenamels from which'insulated wires and other coated products are made, for bonding or cementing together mica flakes to form a laminated mica article, for bonding together abrasive grains in the production of resin-bonded abrasive articles such, for instance, as grindstones, sandpapers, etc., in the manufacture of electrical resistors, etc. They also may be employed for treating cotton, linen and other cellulosic materials in sheet or other form. They alsomay be employed as impregnants for electrical coils and for other electrically insulating applications.

What I claim as new and desire to secure by Letters Patent of the United States is:

1. A composition of matter comprising the re action product of ingredients comprising an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 an aldehyde to condense with a salt (organic or inorganic) of the triazine derivative or with a mixture of the triazine derivative and a salt thereof. Examples of organic and inorganic acids that may be used in the preparation of such salts are hydrochloric, sulfuric, phosphoric, boric, acetic, chloroacetic, propionic, butyric, valeric, acrylic, polyacrylic, oxalic methacrylic, polymethacrylic, malonic, succimc, adipic, malic, maleic, fumaric, benzoic, salicylic, phthalic, camphoric, etc.

Dyes, pigments, plasticizers, mold lubricants, opacifiers and various fillers (e. g., wood flour, glass fibers, asbestos, including defibrated asbestos, mineral wool, mica, cloth cuttings, etc.) may be compounded with the resin in accordance with conventional practice to provide various thermoplastic and thermosetting molding compositions.

and not more than'3, a: is an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, and R. represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon redicals.

2. A composition as in claim 1 wherein the aldehyde is formaldehyde.

3. A composition as in claim 1 wherein the reaction product is an alkaline-catayzed reaction product of the stated components.

4. A composition of matter comprising the reaction product of ingredients comprising an aldehyde and a compound corresponding to the general formula NHR Y where n represents an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, and Z represents a member of the class consisting of oxygen and sulfur.

6. A composition as in claim wherein Z represents oxygen.

7. A heat-curable resinous composition comprising a heat-convertible condensation product of ingredients comprising formaldehyde and a compound corresponding to the general formula l .1 in. isaaml where n represents an integer and is at least 1 and not more than 3, z is an integer and is at least 1 and not more than 2; and Z represents a member of the class consisting of oxygen and sulfur.

8. A product comprising the cured resinous composition of claim 7.

9. A composition comprising the resinous product of reaction of ingredients comprising an aidehyde and s-triazinyl-2,4,6 tri (thio acetyl urea).

10. A composition comprising the resinou product of reaction of ingredients comprising an aldehyde and monoamino s-triazinyl (ii-(thio acetyl urea).

11. A composition comprising the resinous product of reaction of ingredients comprising an aldehyde and diamino s-triazinyl thio acetyl urea.

12. A composition comprising the product of reaction of ingredients comprising a urea, an aldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, and R. represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

13. A composition a in claim 12 wherein the urea component is the compound corresponding to the formula NHzCONHz and the aldehyde is formaldehyde.

14. A composition comprising the product of reaction of ingredients comprising an alcohol, an aldehyde and a compound corresponding to the general formula s 1 z z e, 1 N lamaanalsnl where n represents an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, Z represents a member of the class consisting of oxygen and sulfur, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

15. A heat-curable composition comprising the heat-convertible resinous reaction product of (1) a partial condensation product of ingredients comprising formaldehyde and a compound corresponding to the general formula where n represents an integer and is at least 1 and not more than 3, a: is an integer and is at least 1 and not more than 2, and Z represents a member of the class consisting of oxygen and sulfur, and (2) a curing reactant.

16. A composition as in claim 15 wherein the curing reactant is a chlorinated acetamide.

17. A resinous composition comprising the product of reaction of ingredients comprising urea, formaldehyde and diamino s-triazinyl thio acetyl urea.

18. A composition comprising the resinous product of reaction of ingredients comprising a methylol urea and diamino s-triazinyl thio acetyl urea.

19. A composition comprising the resinous reaction product of a plurality of reactants including melamine, formaldehyde and diamino s-triazinyl thio acetyl urea.

20. The method of preparing new synthetic compositions which comprises eil'ecting reaction between ingredients comprising an aldehyde and a compound corresponding to the general formula m ]r z 1 us i s srtmtsn] L v J where n represents an integer and is at least 1 and not more than 3. :c is an integer and is at least 1 and not morethan 2, Z represents a member of the class consisting of oxygen and sulfur, and R represents a member of the class consisting of hydrogen and monovalent hydrocarbon and halo-hydrocarbon radicals.

GAETANO F. DALELIO.

CERTIFICATE OF' CORRECTION. Patent No. 2,52 2%. July 15, 1915.

GAETANO D'ALELIO.

It is hereby certified that error appears in the printed specification of the" above numbered patent requiring correction as follows: Page 2, second column, line 7, for "N-beta-thio" read- N-(beta-thio page 5, second column, line 1, for "thionacetyl" read -thionoacety1; line 2, for "thioura" read --thiourea-; page 5, first column, line "(0, for' Example" read --Examples-; and second column, line 7,before "0.5 N) insert an opening parenthesis; page 7, first column, line 52, after "1914.1" insert a comma; line 50, for "polvinyl" read --polyviny1; and second column, line 11.5, for "radicals" read --radicals-; line 11.7, for"cate.yzed' read "catalyze d-; and that the said Letters Patent should be read with this correction therein that the same ma conform to the record of the case in the Patent Office Signed and sealed this 21st day of September, A. D. 191 .5.

Henry Van Arsdale,

(Seal) Acting Commissioner of Patents. 

